CN103917547B - Based on the novel organic phosphorus compound of anthracene triol - Google Patents

Based on the novel organic phosphorus compound of anthracene triol Download PDF

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CN103917547B
CN103917547B CN201280054010.2A CN201280054010A CN103917547B CN 103917547 B CN103917547 B CN 103917547B CN 201280054010 A CN201280054010 A CN 201280054010A CN 103917547 B CN103917547 B CN 103917547B
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hydrogen
iii
branched
straight
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CN103917547A (en
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A.克里斯琴森
R.弗兰克
D.弗里达格
D.黑斯
B.克赖德勒
D.泽伦特
A.伯尔纳
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Evonik Operations GmbH
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Evonik Degussa GmbH
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
    • C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
    • C07C45/505—Asymmetric hydroformylation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
    • C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
    • C07F9/6574—Esters of oxyacids of phosphorus
    • C07F9/65746—Esters of oxyacids of phosphorus the molecule containing more than one cyclic phosphorus atom
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2282—Unsaturated compounds used as ligands
    • B01J31/2295—Cyclic compounds, e.g. cyclopentadienyls
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
    • C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System compounds of the platinum group
    • C07F15/0073—Rhodium compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System compounds of the platinum group
    • C07F15/0073—Rhodium compounds
    • C07F15/008—Rhodium compounds without a metal-carbon linkage

Abstract

The present invention relates to multiple product and they as catalytic activity composition the purposes in the method for preparing aldehydes.

Description

Based on the novel organic phosphorus compound of anthracene triol
The present invention relates to the bis-phosphite and the GW-540 that comprise at least one structural element based on anthracene triol, andAnd also relate to its metal complex, preparation and described bis-phosphite and GW-540 in catalytic reaction as multiple toothizationThe purposes of compound.
In the situation that catalyst exists, between olefin(e) compound, carbon monoxide and hydrogen, form and there are many carbon atomsThe reaction of aldehyde be called as hydroformylation or oxo alcohol (Oxierung). The catalyst using in these reactions is logicalIt is often the compound of the compound of the group VIII transition metal of the periodic table of elements, particularly rhodium and cobalt. Use rhodium compoundHydroformylation with use cobalt catalysis to compare, conventionally provide compared with the advantage of high selectivity and to cause product to have higher attachedAdd value. The hydroformylation of rhodium catalysis uses by rhodium and the group preferably forming as the trivalent phosphorous compound of ligand conventionallyCompound. Known ligand is for example from containing respectively three valent phosphors PIIIThe type of phosphine, phosphite ester and phosphinate. AlkeneThe hydroformylation of hydrocarbon is at B.CORNILS, " the AppliedHomogeneousCatalysis of W.A.HERRMANNWithorganometallicCompounds ", Vol.1&2, VCH, Weinheim,, there is summary in New York in 1996.
Every kind of catalytic activity composition based on cobalt or rhodium has its distinctive advantage. Shown in following example,Depend on that raw material and target product use different catalytic activity compositions thus: with rhodium and triphenylphosphine, alpha-olefin canHydroformylation under relatively low pressure. As the common excessive use of triphenylphosphine of phosphorous ligand, requirement simultaneouslyHigh ligand/rhodium ratio is to have increased access to the reaction selectivity of n-aldehyde product of commercial expectation.
Patent US4694109 and US4879416 have described two phosphine ligands and they are under low synthesis gas pressureApplication in olefin hydroformylation. The ligand of the type particularly provides height in the hydroformylation of propyleneActive and high just/different selective. WO95/30680 discloses bidentate phosphine ligand and they especially exist in catalytic reactionApplication in hydrogenation formyl reaction. For example, in patent US4169861, US4201714 and US4193943Two phosphines as the ferrocene-bridging of the ligand for hydroformylation have been described.
The shortcoming of bidentate and multiple tooth phosphine ligand is that their preparation is relative very loaded down with trivial details. Therefore, in commercial run, useThis system is often infeasible economically. Also have relatively low reactivity, this relatively low reactivity is in skillIn art, must compensate by the high time of staying. This so cause the less desirable side reaction of product.
Rhodium-mono-phosphite ester complex in catalytic activity composition is for the adding of branched-chain alkene with internal double bondsHydrogen formylation is applicable to, but selectively low with regard to the compound of end hydroformylation. EP0155508 public affairsOpen single phosphite ester of two arlydene-replacements at steric hindrance alkene, for example, in the hydroformylation of the rhodium-catalysis of isobuteneApplication.
Catalytic activity composition based on rhodium-bis-phosphite complex is applicable to have the straight chain of end and internal double bondsThe hydroformylation of alkene, wherein mainly produces the product of end hydroformylation. By contrast, there is internal double bondsBranched-chain alkene only transforms less amount. These phosphite esters provide urging of enhanced activity in the time that it is coordinated to transition metal centerAgent, but the running life of these catalytic activity compositions can not be satisfactory, especially due to phosphite ester ligand pairIn the sensitiveness of hydrolysis. The diaryl glycol replacing as construction unit for phosphite ester ligand, as at EP0214622 or EP0472071 as described in, produced significant improvement.
In document, say, the catalytic activity composition of these ligands based on rhodium is in the hydroformylation of alpha-olefinExtremely activated. Patent US4668651, US4748261 and US4885401 have described poly-phosphite ester coordinationBody, uses this ligand, and alpha-olefin and 2-butylene can be converted into high selectivity the product of end hydroformylation. This kindThe bidentate ligand of type has also been used to hydroformylation butadiene (US5312996).
Bis-phosphite is disclosed in EP1294731, in the time using in the hydroformylation in octene mixture,Olefin conversion up to 98% is provided. But 36.8% to just selective to aldehyde C-9 that mostly is most 57.6% same expectation(n-Selektivit is t) need to be improved. This is suitable for more because in commercial run catalytic activity compositionThe running life of application requirements a couple of days but not a few hours.
Although mentioned bis-phosphite is for the hydroformylation catalysts based on rhodium and the ligand of Yan Shihao,But development of new ligand is desirable.
These novel ligands should:
● in thering is the alkene of internal double bonds or containing the hydroformylation of alkene mixture, there is high just selectionProperty, that is, and isomerization characteristic;
● also have intrinsic catalyst poison, the resistance of the improvement of for example water, and ought be used in thus catalytic activity combinationDuring for hydroformylation can be provided in thing the running life of prolongation;
● and suppress rhodium known aggregation formability in catalytic activity composition, and ought be used in and urge thusThe running life of again realizing prolongation while changing in active compound for hydroformylation.
These targets realize by compound according to the present invention, and compound according to the present invention comprises structural element(I):
And,
-described compound comprises at least two O-PIIIKey, wherein these O-PIIIKey can produce from identical PIIIOrProduce from different PIII；
If-structural element (I) occurs twice in described compound, they pass through C10-C10 ' carbon bond or pass through soFollowing X1-G1-X2Unit is connected to each other:
Wherein X1Be connected to the P of the first structural element (I)III, and X2Be connected to the P of the second structural element (I)III，
Wherein G1=there is the straight or branched of the further replacement of any hope, aliphatic series or aromatics or heteroaromatic or condenseThe alkyl of aromatics or fused aromatic-heteroaromatic;
Wherein X1、X2Be selected from: O, NY1、CY2Y3；
Can be wherein X1And X2The implication of selecting is independently each other;
Wherein Y1、Y2、Y3Be selected from hydrogen, replacement or unsubstituted aliphatic series, alkyl replacement or unsubstituted aromatics;
Can be wherein each Y1-Y3The implication of selecting is independently each other;
Wherein Y1-Y3Two or morely can covalently connect each other;
Wherein R1、R2、R3、R4、R5、R6、R7Be selected from: hydrogen, replacement or unsubstituted, straight or branched, aliphatic or fragrantThe alkyl of family; F, Cl, Br, I ,-OR8、-C(O)R9、-CO2R10、-CO2M1、-SR11、-SOR12、-SO2R13、-SO3R14、-SO3M2、-NR15R16；
Wherein R8、R9、R10、R11、R12、R13、R14、R15、R16Be selected from: hydrogen, replacement or unsubstituted, straight or branched, the alkyl of aliphatic series or aromatics or heteroaromatic or fused aromatic or fused aromatic-heteroaromatic;-OR17；
Wherein R17Be selected from: hydrogen, unsubstituted or replacement, straight or branched, the alkyl of aliphatic series or aromatics; Wherein R1-R17Two or morely can covalently connect each other;
Wherein M1And M2Be selected from: alkali metal, alkaline-earth metal, An, Phosphonium and
Can be wherein M1And M2The implication of selecting is independently each other.
In one embodiment of the invention, described compound comprises structural element (II):
Wherein
W is selected from:
-hydrogen;
-there is aliphatic series, aromatics, heteroaromatic, fused aromatic, the fused aromatic-heteroaromatic of the further replacement of any hopeAlkyl;
-PIII(G2)(G3) group:
Wherein G2And G3Be selected from respectively: hydrogen; There is the straight or branched of the further replacement of any hope, aliphatic or fragrantThe alkyl of family or heteroaromatic or fused aromatic or fused aromatic-heteroaromatic; F, Cl, Br, I or-OR18、-C(O)R19、-CO2R20、-CO2M1、-SR21、-SOR22、-SO2R23、-SO3R24、-SO3M2、-NR25R26；
Wherein R18、R19、R20、R21、R22、R23、R24、R25、R26Be selected from: hydrogen, replacement or unsubstituted, straight or branched, the alkyl of aliphatic series or aromatics;-OR27；
Wherein R27Be selected from: hydrogen, replacement or unsubstituted, straight or branched, the alkyl of aliphatic series or aromatics; F, Cl, Br,I；
Wherein M1And M2Be selected from: alkali metal, alkaline-earth metal, An, Phosphonium and
Can be wherein M1And M2The implication of selecting is independently each other;
Can be wherein G2And G3The implication of selecting is independently each other, and G2And G3Each other can covalencyGround connects,
-SiR28R29R30; Wherein R28、R29、R30=hydrogen; There is the straight or branched of the further replacement of any hope, the alkyl of aliphatic series or aromatics or heteroaromatic or fused aromatic or fused aromatic-heteroaromatic; Can be wherein R28、R29And R30ChoosingThe implication of selecting is independently each other, and R wherein28And R29Can covalently connect each other.
In one embodiment of the invention, described compound comprises structural element (III):
Wherein Z represents G4Or X1-G1-X2Unit,
And G4Be selected from: hydrogen; There is the straight or branched of the further replacement of any hope, aliphatic series or aromatics or assortedThe alkyl of aromatics or fused aromatic or fused aromatic-heteroaromatic; F, Cl, Br, I Huo – OR31、-C(O)R32、-CO2R33、-CO2M1、-SR34、-SOR35、-SO2R36、-SO3R37、-SO3M2、-NR38R39，
Wherein R31、R32、R33、R34、R35、R36、R37、R38、R39Be selected from: hydrogen, replacement or unsubstituted, straight or branched, the alkyl of aliphatic series or aromatics;-OR40；
Wherein R40Be selected from: hydrogen, replacement or unsubstituted, straight or branched, the alkyl of aliphatic series or aromatics;
Wherein M1And M2Be selected from: alkali metal, alkaline-earth metal, An, Phosphonium and
Can be wherein M1And M2The implication of selecting is independently each other.
In one embodiment of the invention, described compound comprises structural element (IV):
Wherein G5And G6Be selected from: hydrogen; There is the straight or branched of the further replacement of any hope, aliphatic series or aromatics orThe alkyl of heteroaromatic or fused aromatic or fused aromatic-heteroaromatic; F, Cl, Br, I or-OR41、-C(O)R42、-CO2R43、-CO2M1、-SR44、-SOR45、-SO2R46、-SO3R47、-SO3M2、-NR48R49，
Wherein R41、R42、R43、R44、R45、R46、R47、R48、R49Be selected from: hydrogen, replacement or unsubstituted, straight or branched, the alkyl of aliphatic series or aromatics;-OR50；
Wherein R50Be selected from: hydrogen, replacement or unsubstituted, straight or branched, the alkyl of aliphatic series or aromatics;
Wherein M1And M2Be selected from: alkali metal, alkaline-earth metal, An, Phosphonium and
Can be wherein M1And M2The implication of selecting is independently each other,
Can be wherein G5And G6The implication of selecting is independently each other, and G5And G6Each other can covalencyGround connects.
In one embodiment of the invention, W represents PIII(G2)(G3) group.
In one embodiment of the invention, G2、G3=-OR18。
In one embodiment of the invention, G5、G6=-OR41。
In one embodiment of the invention, X1、X2=O。
In one embodiment of the invention, G1Comprise two arlydene of the further replacement with any hope.
In one embodiment of the invention, G1Comprise structural element (V):
Wherein R51、R52、R53、R54、R55、R56、R57、R58=hydrogen; Have any hope further replacement straight chain orChain, the alkyl of aliphatic series or aromatics or heteroaromatic or fused aromatic or fused aromatic-heteroaromatic; F, Cl, Br or I; Or-OR59、-COR60、-CO2R61、-CO2M1、-SR62、-SOR63、-SO2R64、-SO3R65、-SO3M2、-NR66R67, or N=CR68R69; ItsIn can be each R51-R58The implication of selecting is independently each other, and R wherein51-R58Two or more each other itBetween can covalently connect;
Wherein R59、R60、R61、R62、R63、R64、R65、R66、R67Be selected from: hydrogen, replacement or unsubstituted, straight or branched, the alkyl of aliphatic series or aromatics;-OR68；
Wherein R68Be selected from: hydrogen, replacement or unsubstituted, straight or branched, the alkyl of aliphatic series or aromatics;
Wherein M1And M2Be selected from: alkali metal, alkaline-earth metal, An, Phosphonium and
Can be wherein M1And M2The implication of selecting is independently each other,
And there is a and b as being connected to X1And X2Tie point.
In one embodiment of the invention, G2And G3Covalently connect each other.
In one embodiment of the invention, connect G2-G3Comprise following structural element (VI):
Wherein R69、R70、R71、R72、R73、R74、R75、R76=hydrogen; Have any hope further replacement straight chain orSide chain, the alkyl of aliphatic series or aromatics or heteroaromatic or fused aromatic or fused aromatic-heteroaromatic; F, Cl, Br or I; Or-OR77、-COR78、-CO2R79、-CO2M1、-SR80、-SOR81、-SO2R82、-SO3R83、-SO3M2、-NR84R85, or N=CR86R87; ItsIn can be each R69-R76The implication of selecting is independently each other, and R wherein69-R76Two or more each other itBetween can covalently connect;
Wherein R77、R78、R79、R80、R81、R82、R83、R84、R85Be selected from: hydrogen, replacement or unsubstituted, straight or branched, the alkyl of aliphatic series or aromatics;-OR86；
Wherein R86Be selected from: hydrogen, replacement or unsubstituted, straight or branched, the alkyl of aliphatic series or aromatics;
Wherein M1And M2Be selected from: alkali metal, alkaline-earth metal, An, Phosphonium and
Can be wherein each M1And M2The implication of selecting is independently each other.
In one embodiment of the invention, G5And G6Covalently connect each other.
In one embodiment of the invention, connect G5-G6Comprise following structural element (VII):
Wherein R87、R88、R89、R90、R91、R92、R93、R94=hydrogen; Have any hope further replacement straight chain orChain, the alkyl of aliphatic series or aromatics or heteroaromatic or fused aromatic or fused aromatic-heteroaromatic; F, Cl, Br or I; Huo –OR95、-COR96、-CO2R97、-CO2M1、-SR98、-SOR99、-SO2R100、-SO3R101、-SO3M2、-NR102R103, or N=CR104R105; Can be wherein each R31-R38The implication of selecting is independently each other, and R wherein86-R93Two orMultiplely can covalently connect each other;
Wherein R95、R96、R97、R98、R99、R100、R101、R102、R103Be selected from: hydrogen, replacement or unsubstituted, straight chain orChain, the alkyl of aliphatic series or aromatics;-OR104；
Wherein R104Be selected from: hydrogen, replacement or unsubstituted, straight or branched, the alkyl of aliphatic series or aromatics; Wherein M1And M2Be selected from: alkali metal, alkaline-earth metal, An, Phosphonium and
Can be wherein M1And M2The implication of selecting is independently each other.
In one embodiment of the invention, PIII(G2)(G3) group according to structural formula corresponding to PIII(G5)(G6) baseGroup.
Except compound self, the also claimed complex that comprises such compound.
In one embodiment of the invention, complex comprises compound and at least one center gold as described aboveBelong to atom, wherein said compound is by least one PIIIBe coordinated on central metal atom.
In one embodiment of the invention, central metal atom is selected from the 8-10 family of the periodic table of elements.
In a preferred embodiment of the invention, central metal atom is rhodium.
Except complex self, the also claimed composition that contains such complex.
In one embodiment, described composition contains and is not coordinated on central metal atom as described aboveCompound and as described above complex.
Except composition, also claimed its purposes.
In one embodiment, described composition is used as catalytic activity composition in organic compound synthetic.
In one embodiment, described composition is in the side of the hydroformylation for ethylenically unsaturated hydrocarbons mixtureIn method, be used as catalytic activity composition.
Also claimed multi-phase reaction mixture.
In one embodiment, multi-phase reaction mixture comprises ethylenically unsaturated hydrocarbons mixture, contain carbon monoxide andThe admixture of gas of hydrogen, aldehydes, as described above as the composition of catalytic activity composition.
Also the claimed hydroformylation for ethylenically unsaturated hydrocarbons mixture is to prepare the method for aldehydes.
In a modification, this method comprises the following steps:
A) provide the mixture of ethylenically unsaturated hydrocarbons class;
B) add catalytic activity composition as described above;
C) introduce the mixture that comprises carbon monoxide and hydrogen;
D) heat the temperature range of this reactant mixture to 80 DEG C-120 DEG C;
E) pressure limit of construction 1.0MPa-6.4MPa;
F) finishing to isolate ethylenically unsaturated hydrocarbons mixture after reaction.
In a modification of the method, the method comprises following additional step:
G) unconverted ethylenically unsaturated hydrocarbons mixture is isolated and is back to step a) in.
In a modification of the method, the method comprises following additional step:
H) described catalytic activity composition is isolated and is back to step b) in.
In a modification of the method, the method comprises following additional step:
I) the unconverted admixture of gas containing carbon monoxide and hydrogen is isolated and is back to step c) in.
Now by the illustrative embodiment illustrating according to compound of the present invention:
Have two phosphorus atoms according to the illustrative embodiment of bidentate compound of the present invention:
。
Have three phosphorus atoms according to the illustrative embodiment of tridentate compounds of the present invention:
。
Have four phosphorus atoms according to the illustrative embodiment of four tooth compounds of the present invention:
。
The composite traces of selected compounds
Compound 1
The suspension of 1,8,9-anthracene triol (0.3549g, 1.5686mmol) in toluene (6ml) is 0 DEG C and stirringLower and triethylamine (0.69ml, 4.939mmol) mixes, and then dropwise drips 4,8-bis--tert-butyl-6-chloro-2,10-bis-Methoxyl group dibenzo [d, f] [1,3,2] dioxa-phospha ring in heptan (phosphepin) (1.3267g, 3.1372mmol) existsSolution in toluene (15ml). This mixture is stirred and spends the night and filter, filtrate is concentrated into dry in a vacuum. ResidueUnder 40 DEG C and 0.1KPa dry 2 hours and (mobile phase is carrene, R by column chromatography purifyingf=0.62). Productive rate:1.39g (1.39mmol; 89%). Elementary analysis is (to C58H64O11P2=999.08g/mol calculates): C70.17(69.73)；H6.50(6.46)；P6.07(6.20)%。1HNMR(CD2Cl2):δ0.95-1.59(36H)，(3.76-3.88 8 signals, 12H); 4.68-5.27 (1H); 6.24-8.00 (15H). Diastereoisomer ratio=1:5. CI-MS:(iso-butane, cation) m/e1055 (18%, M++i-C4H8)，999(63%、M+)。
Compound 2
The suspension of 1,8,9-anthracene triol (1.076g, 4.755mmol) in toluene (18ml) 0 DEG C and stir underMix with triethylamine (2.09ml, 14.973mmol), then dropwise drip 2,4,8,10-, tetra--tert-butyl-6-chlorodiphenyl alsoThe solution of [d, f] [1,3,2] dioxa phospha ring in heptan (4.518g, 9.511mmol) in toluene (45ml). By this mixingThing at room temperature stirs and spends the night and at 70 DEG C, react 2 hours in addition, filters, and filtrate is concentrated into dry in a vacuum. RemainingThing is by column chromatography prepurification (mobile phase/hexanes/ch=1:2, Rf=0.72), thick productive rate is 4.27g(3.869mmol, 81%). Recrystallization by hot acetonitrile obtains pure material. Elementary analysis is (to C70H88O7P2=1103.41g/Mol calculates): C76.00 (76.20), H7.86 (8.04), P5.41 (5.61) %.1HNMR(CD2Cl2):δ0.80-1.45 (72H), 4.62-5.13 (1H), 5.69-7.84 (15H) ppm. CI-MS (iso-butane, cation:m/e1103(100%、M+)。
Compound 3
The suspension of anthracene triol (0.629g, 2.782mmol) in toluene (14ml) 0 DEG C and stir under with three secondAmine (0.866g, 8.76mmol) mixes, and then dropwise drips 4,8-, bis--tert-butyl-2,6,10-trichlorine dibenzo [d, f]The solution of [1,3,2] dioxa phospha ring in heptan (2.611g, 5.563mmol) in toluene (26ml). This mixture is stirredMix and spend the night and filter, filtrate is concentrated into dry in a vacuum. Hexane (65ml) recrystallization obtains the product (about of enrichment85%), it is for further synthetic. Productive rate: 1.479g (1.455mmol; 52%).31PNMR(CD2Cl2):δ102.8(s，br)，105.5(s，br)，136.5(s，br)，138.3(s，br)ppm。
Compound 4
Under agitation, at-20 DEG C by 1,8,9-anthracene triol (0.207g, 0.928mmol) and triethylamine (0.294G, 2.92mmol) solution in toluene (10ml) and compound 24 (0.882g, 0.928mmol) be at toluene (10ml)In solution mix, wherein the solution of compound 24 in toluene dropwise drips. After at room temperature stirring is spent the night, filter anti-Answer solution, filtrate is concentrated into dry in a vacuum. The solid matter obtaining is dried 2 hours under 50 DEG C/0.1KPa, and usesAcetonitrile (100ml) recrystallization. Productive rate: 0.391g (0.411mmol, 44%). Elementary analysis is (to C70H88O7P2=1103.40g/mol calculates): C75.16 (76.20); H8.25 (8.04); P5.43 (5.61) %.31PNMR(CD2Cl2):δ102.8(s，br)，109.8(s，br)，142.2(s，br)，142.7(d，JPP=6Hz) ppm. By, there are two kinds of diastereomer products in NMR spectrum. EI-MS:m/e1102 (5%, M+)。
Compound 5
-20 DEG C and stir under by 1,8,9-anthracene triol (0.538g; 2.378mmol) and triethylamine (0.757g,7.49mmol) the solution in toluene (20ml) and 21 (2.011g, 2.378mmol) (30ml) molten in tolueneLiquid mixes, and 21 solution in toluene dropwise drip. After under room temperature, stirring is spent the night, filtering reacting solution, filtrate is in vacuumIn be concentrated into dry. The solid matter obtaining is dried 2 hours under 50 DEG C/0.1KPa, and uses column chromatography purifying (wash-outLiquid: carrene, Rf=0.46 and 0.51, two kind of diastereoisomer). Productive rate: 1.263g (1.264mmol; 53%).Elementary analysis is (to C58H64O11P2=999.08g/mol calculates): C68.96 (69.73), H6.28 (6.46), P6.17(6.20)%。31PNMR(CD2Cl2):δ104.3(d，JPP=37Hz)；108.5(d，JPP=37Hz)，138.4(s，br)；140.5(s，br)ppm.EI-MS:m/e998(2%，M+)。
Compound 6
The solution of 5 (0.994g, 0.995mmol) in THF (7ml) be dissolved in six in THF (12ml)Methyl disilazane (0.802g, 4.98mmol) mixes. Reaction solution is added to hot reflux 10 hours, then concentrated in a vacuumTo dry. The solid matter obtaining is dried 2 hours under 50 DEG C/0.1KPa. Residue is recrystallized with hexane. Productive rate: 0.877g(0.819mmol，82%)。1HNMR(CD2Cl2):δ0.15-1.31(45H)，3.62-3.81(12H)，6.17-7.94(m，15H)ppm。
Compound 7
The solution of 1 (0.966g, 0.967mmol) in toluene (12ml) under the gentle agitation of chamber with triethylamine(0.42ml, 3.035mmol) mixes, and then at 0 DEG C, oneself encircles with 2-chloro-4H-benzo [d] [1,3,2] dioxa phospha(phosphinin) solution of-4-ketone (0.196g, 0.967mmol) in toluene (4ml) mixes. By reactant mixture literTemperature, to room temperature, stirs and spends the night and filter. Filtrate is concentrated into dry in a vacuum, and residue is dry 3 little under 40 DEG C/0.1KPaTime, then by column chromatography purifying (mobile phase hexanes/ch, 1:10, Rf=0.8). Productive rate: 1.095g(0.939mmol, 97%). Elementary analysis is (to C65H67O14P3=1165.15g/mol calculates): C67.50 (67.01), H5.80(5.80)，P8.04(7.97)%。1HNMR(CD2Cl2):δ1.08-1.65(36H)，3.68-3.94(12H), 6.10-8.10 (19H) ppm. ESI-TOFHRMS (MeOH/0.1%HCOOH is 90:10 in water) m/e1187.3633(100%，M+Na)+。
Compound 8
The solution of 1 (2.0g, 2.002mmol) in toluene (20ml) under the gentle agitation of chamber with triethylamine (0.88Ml, 6.314mmol) mix, but at 0 DEG C with the own ring-4-of 2-chloro-4H-naphtho-[1,2-d] [1,3,2] dioxa phosphaThe solution of ketone (0.656mg, 2.602mmol) in toluene (7ml) mixes. Reactant mixture is warming up to room temperature, stirsSpend the night and filter. Filtrate is concentrated into dry in a vacuum, and residue is dried 1 hour under 50 DEG C/0.1KPa, then uses post lookSpectrometry purifying (mobile phase hexanes/ch, 1:10, Rf=0.62). Productive rate: 2.07g (1.703mmol, 85%). UnitElement is analyzed (to C69H69O14P3=1215.21g/mol calculates): C68.05 (68.20), H5.85 (5.72), P7.27(7.65)%。1HNMR(CD2Cl2):δ1.09-1.65(36H)，3.66-3.96(12H)，6.11-8.24(21H)Ppm. CI-MS (iso-butane, cation): m/e1214 (1%, M+)，1044。
Compound 9
The solution of 2 (1.329g, 1.204mmol) in toluene (15ml) under the gentle agitation of chamber with triethylamine(0.53ml, 3.781mmol) mixes, but oneself encircles with 2-chloro-4H-benzo [d] [1,3,2] dioxa phospha at 0 DEG C-The solution of 4-ketone (0.243mg, 1.204mmol) in toluene (5ml) mixes. Reactant mixture is warming up to room temperature, stirsMix 48 hours and filter. Filtrate is concentrated into dry in a vacuum, and residue is dried 1 hour under 50 DEG C/0.1KPa, then usesColumn chromatography purifying (mobile phase hexanes/ch, 2:1, Rf=0.22). Productive rate: 1.14g (0.898mmol, 74%).Elementary analysis is (to C77H91O10P3=1269.48g/mol calculates): C73.07 (72.85), H7.25 (7.23), P7.37(7.32)%.31PNMR(CD2Cl2):δ102.5-103.7(1P)，118.5-119.8(1P)，135.6-136.3(1P)ppm。EI-MS:m/e1268(38%，M+-H)，1085(43%)。
Compound 10
A) available from 2-hydroxy niacin, 2-chloro-4H-[1,3,2] also [4,5-b] pyridine-4-ketone of oneself ring of dioxa phosphaChloro phosphite ester
2-hydroxy niacin (0.5g, 3.594mmol) and triethylamine (1.5ml, 10.783mmol) are at THF (20Ml) solution under agitation mixes with the PCl3 (0.494g, 3.594mmol) being dissolved at-20 DEG C in THF (8ml)Close. At room temperature stir and spend the night and at 70 DEG C, stir 2 hours, filtering reacting solution is also used THF (5ml) washing solidsMatter. Filtrate is concentrated into dry in a vacuum, and yellow residue is dried 1 hour under 50 DEG C/0.1KPa. Productive rate: 0.519g(2.550mmol, 71%). Solid matter has the purity of 95mol% according to NMR spectrum, and use in next step syntheticAnd there is no further purifying.
1HNMR(CD2Cl2):δ7.37(dd，1H)，8.40(dd，1H)，8.53(dd，1H)ppm。
B) be converted into the reaction of compound 10
1 (1.859g, 1.861mmol) in toluene the solution of (22ml) under the gentle agitation of chamber with triethylamine(0.82ml, 5.869mmol) mixes, then at 0 DEG C with 2-chloro-4H-[1,3,2] oneself ring [4,5-also of dioxa phosphaB] the solution mixing of pyridine-4-ketone (0.4544g, 2.233mmol) in toluene (14ml). Mixture is warming up to chamberTemperature, stirs and spends the night and filter, with THF (2 × 4ml) washing leaching cake. The filtrate merging is concentrated into dry in a vacuum, andUnder 50 DEG C/1mbar, be dried 3 hours. Residue stirs and spends the night with 50ml hexane. After filtration, distill in a vacuum desolventizing,The solid matter obtaining is dried 5 hours under 70 DEG C/0.1KPa. Productive rate: 2.00g (1.715mmol, 92%). Element dividesAnalyse (to C64H66O14NP3=1166.14g/mol calculates): C64.48 (65.92), H5.70 (5.70), P7.98(7.97)，N1.36(1.20)1HNMR(CD2Cl2):δ0.77-1.62(36H)，3.56-3.74(12H)，5.89-8.44(18H)ppm。EI-MS:m/e1165(13%，M+)。
Compound 11
The solution of 22 (2.135g, 1.941mmol) in toluene (18ml) under the gentle agitation of chamber with triethylamine(1.08ml, 7.765mmol) mixes, then at 0 DEG C with solid 1,8,9-anthracene triol (0.439g, 1.941mmol) is mixedClose. Mixture is warming up to room temperature, stirs and spend the night and filter, except desolventizing, residue is under 50 DEG C/0.1KPa in a vacuumDry 5 hours. Productive rate: 2.35g (1.875mmol, 96%). Elementary analysis is (to C72H71O14P3=1253.26g/molCalculate): C69.18 (69.00), H5.86 (5.71), P7.34 (7.42) %.1HNMR(CD2Cl2):δ0.77-1.46(36H)，3.41-3.71(12H)；5.78-8.42(22H)，12.06-12.76(1H)ppm。EI-MS:m/e1253(2%，M+)，999(100%)。
Compound 12
The solution of 22 (1.082g, 0.983mmol) in toluene (10ml) under the gentle agitation of chamber with triethylamine(0.55ml, 3.934mmol) mix, then at 0 DEG C with solid 1,9-anthracene glycol (0.207g, 0.983mmol) mix.Mixture is warming up to room temperature, stirs and spend the night and then stir 2 hours at 70 DEG C, filter, in a vacuum except desolventizing, residueUnder 60 DEG C/0.1KPa, be dried 4 hours. Residue is purified (dichloromethane/hexane=1:1, Rf=by column chromatography0.27). Productive rate: 0.931g (0.752mmol, 76%). Elementary analysis is (to C72H71O13P3=1237.26g/mol meterCalculate): C69.77 (69.90), H5.93 (5.78), P7.52 (7.51) %.1HNMR(CD2Cl2):δ0.90-1.65(36H)，3.61-3.91(12H)，6.05-8.28(23H)ppm。EI-MS:m/e1238(11%，M+)，982(43%)，579(100%)。
Compound 13
The solution of 11 (0.674g, 0.537mmol) in THF (4ml) dropwise with HMDS (0.433G, 2.689mmol) solution in THF (8ml) mixes, and refluxes 14 hours, is then concentrated into dry. Residue post lookSpectrometry purifying (eluent hexanes/ch, 1:2, Rf=0.47). Productive rate: 0.482g (0.364mmol, 68%). UnitElement is analyzed (to C75H79O14P3Si=1325.44g/mol calculates): C67.59 (67.96), H6.09 (6.01), P6.89(7.01)，Si2.15(2.12)%。1HNMR(CD2Cl2):δ0.00-1.53(45H)，3.20-3.75(12H), 5.88-7.91 (22H) ppm. According to NMR spectrum, there are two kinds of diastereomer products. ESI/TOF-HRMS:m/e1325.45076(M+H)+。
Compound 14
Molten in toluene (5ml) of 23 (0.47g, 0.390mmol) and triethylamine (0.158g, 1.561mmol)Liquid and solid 1,8,9-anthracene triol (0.088g, 0.390mmol) mixes at 0 DEG C. After at room temperature stirring is spent the night, 70At DEG C, stir 2 hours, filtering reacting solution, filtrate is concentrated into dry in a vacuum. Residue is purified (eluent by column chromatographyHexanes/ch, 2:1, Rf=0.4). Productive rate: 0.270g (0.199mmol, 51%). Elementary analysis is (rightC84H95O10P3=1357.58g/mol calculates): C74.30 (74.32), H6.89 (7.05), P6.80 (6.85)%。31PNMR(CD2Cl2):δ103.2(s，br)，104.2(s，br)，104.4(d，JPP=10Hz)，104.7(s，br)，105.3(s)，106.4(d，JPP=10Hz)，135.6(s，br)，136.0(s，br)，136.3(s，br)ppm。According to NMR spectrum, there are three kinds of diastereomer products. ESI/TOF-HRMS:m/e1357.62109 (M+H)+。
Compound 15
3 (1.479g, 1.455mmol) and triethylamine (0.462g, 4.568mmol) are in the toluene (20ml)Solution under agitation with oneself ring-4-ketone (0.338g, 1.673mmol) of 2-chloro-4H-benzo [d] [1,3,2] dioxa phosphaSolution in toluene (10ml) mixes at 0 DEG C. After at room temperature stirring is spent the night, filtering reacting solution, filtrate is in a vacuumBe concentrated into dry. The solid matter obtaining is dried 2 hours under 50 DEG C/0.1KPa, and passes through by acetonitrile recrystallization purifying. ProduceRate: 1.133g (0.958mmol, 66%). Elementary analysis is (to C61H55O10P3Cl4=1182.82g/mol calculates): C61.49(61.94)，H4.71(4.69)，P7.85(7.86)%。1HNMR(CD2Cl2):δ0.82-1.46(36H)，5.98-7.94(19HAromatic ring). According to NMR spectrum, there are six kinds of diastereomer products. EI-MS:m/e1182 (10%, M+)。
Compound 16
The solution of 5 (0.999g, 1mmol) in toluene (12ml) under the gentle agitation of chamber with triethylamine (0.53Ml, 3.781mmol) mix, then at 0 DEG C with oneself ring-4-ketone of 2-chloro-4H-benzo [d] [1,3,2] dioxa phospha(0.203g, 1mmol) solution in toluene (4ml) mixes. Reactant mixture is warming up to room temperature, stirs and spend the night and mistakeFilter. Filtrate is concentrated into dry in a vacuum, and residue is dried 3 hours under 40 DEG C/0.1KPa, then pure by column chromatographyChange (mobile phase hexanes/ch, 1:10, Rf=0.8). Productive rate: 1.107g (0.950mmol, 95%). Elementary analysis(to C65H67O14P3=1165.15g/mol calculates): C67.35 (67.01), H5.80 (5.80), P8.01(7.97) %. (MeOH/0.1%HCOOH is at H for ESI-TOFHRMS290:10 in O) m/e1187.3633 (100%, M+Na)+。
Compound 17
At 0 DEG C, to 1 (1.487g, 1.489mmol) and triethylamine (0.472g, 4.673mmol) at toluene(17ml) oneself encircles (0.333g, 1.489 in the solution in, to add 2-chloro naphtho-[1,8-de] [1,3,2] dioxa phosphaMmol) solution in toluene (10ml). After under room temperature, stirring is spent the night, filtering reacting solution, filtrate is concentrated into dry in a vacuumDry. The solid matter obtaining is dried 2 hours under 50 DEG C/0.1KPa, and is recrystallized by acetonitrile (20ml). Productive rate: 1.087G (0.915mmol, 61%). Elementary analysis is (to C68H69O13P3=1187.20g/mol calculates): C68.67(68.80)，H5.90(5.86)，P7.83(7.83)%。1HNMR(CD2Cl2):δ1.00-1.63(36H)，3.67-3.89(12H)，6.02-8.02(21H)ppm。EI-MS:m/e1187(20%，M+)。
Compound 18
The solution of 1 (1.289g, 1.289mmol) in THF (12ml) at-20 DEG C with equivalent at hexane (5Ml) n-BuLi in mixes. Be warming up to room temperature, stir and spend the night subsequently, thus obtained mixture joins 4,8-at 0 DEG CTwo-tert-butyl-6-chloro-2,10-dimethoxy dibenzo [d, f] [1,3,2] dioxa-phospha ring in heptan (0.545g,1.289mmol) in the solution in THF (9ml). This mixture at room temperature stirs 16 hours and is concentrated in a vacuumDry. Toluene for residue (12ml) stirs and filters, and filtrate is concentrated in a vacuum, and dry residual under 50 DEG C/0.1KPaExcess 3 hours.31PNMR(CD2Cl2):δ102.8，104.4，106.6，109.6，132.8，134.4，134.9，136.9，143.4ppm。
Compound 19
A) by W.Geiger, Chem.Ber.1974, the method described in 107,2976-2984 is synthesized dimerization anthraceneTriol.
B) suspension of anthracene triol dimer (0.298g, 0.6615mmol) in toluene (2ml) under agitation withTriethylamine (0.29ml, 2.083mmol) mix, then at 0 DEG C with 4,8-, bis--tert-butyl-6-chloro-2,10-diformazanMolten in toluene (10ml) of ring in oxygen base dibenzo [d, f] [1,3,2] dioxa phospha heptan (1.119g, 2.646mmol)Liquid mixes, and the latter dropwise adds. Mixture at room temperature stirs and spends the night, and at 70 DEG C, stirs 6 hours in addition and filter,With hot toluene (5ml) cleaning glass matter residue (Frittenr ü ckstand), filtrate is concentrated into dry in a vacuum. SlightlyProductive rate: 0.589g (0.295mmol, 44%). Stirring with acetonitrile (10ml), filter, nature of glass residue is received inTHF (5ml) neutralization adds acetonitrile (8ml) to carry out afterwards crystallization in addition. The solid matter obtaining is dry in a vacuum. Element dividesAnalyse (to C116H126O22P4=1996.15g/mol calculates): C69.48 (69.80), H6.20 (6.36), P6.15(6.21)%。1HNMR(CD2Cl2):δ1.35(36H)，1.37(36H)，3.37(2H)，3.66(12H)，3.71(12H)，5.60-6.93(28H)ppm。ESI/TOF-HRMS:m/e1995.7740(M+)，EI-MS:m/e998 (47%, the homolysis product under the shooting condition of EI-MS).
Compound 20 (× 2 toluene)
The suspension of anthracene triol dimer (0.400g, 0.888mmol) in toluene (28ml) is under agitation with threeEthamine (0.4ml, 2.892mmol) mix, then at-20 DEG C with 21,4,8-, bis--tert-butyl-6-(3,3'-, bis--uncle-Butyl-2'-(dichloro-phosphino-oxygen)-5,5'-dimethoxy-biphenyl base-2-oxygen base)-2,10-dimethoxy dibenzo [d, f][1,3,2] dioxa phospha ring in heptan, (1.488g, 1.776mmol) solution in toluene (32ml) dropwise mixes. MixThing at room temperature stirs and spends the night, and at 70 DEG C, stirs 2 hours in addition and filter, and filtrate is concentrated into dry in a vacuum, remnantsThing is dried 2.5 hours under 50 DEG C/0.1KPa. The acetonitrile for solid matter (40ml) obtaining stirs and spends the night and filter, 50DEG C/0.1KPa under dry 4 hours. Productive rate: 0.757g (0.379mmol, 43%). Elementary analysis is (to C130H142O22P4=2180.28g/mol calculate): C70.91 (71.61), H6.37 (6.56), P5.56 (5.68) %.1HNMR(CD2Cl2):δ0.74-1.45(72H)，3.6-3.7(24H)，6.2-9.1(28H)，11.56-12.13(2H)Ppm. ESI/TOF-HRMS:m/e1996.7820 (M+H-toluene2)+。
Compound 21
4,8-, bis--tert-butyl-6-(3,3'-, bis--tert-butyl-2'-(dichloro-phosphino-oxygen)-5,5'-dimethoxy-biphenylBase-2-oxygen base)-2,10-dimethoxy-dibenzo [d, f] [1,3,2] dioxa phospha ring in heptan
3,3'-, bis--tert-butyl-2'-(4,8-, bis--tert-butyl-2,10-dimethoxy dibenzo [d, f] [1,3,2] twoOxa-phospha ring-6-in heptan oxygen base)-5,5'-dimethoxy-biphenyl base-2-alcohol (by D.Selent, D.Hess, K.-D.Wiese, D.R ttger, C.Kunze, A.B rner, Angew.Chem.2001,113,1739 method preparation)(11.37g, 15.26mmol) and triethylamine (3.09g, the 30.54mmol) solution in toluene (133ml) is stirringDescend and be dissolved in the PCl in toluene (17ml)3(2.51g, 18.31mmol) mixes at 0 DEG C. Under room temperature, stir and spend the nightAfter, at 85 DEG C, stir 3.5 hours, filtering reacting solution, filtrate is concentrated into dry in a vacuum. Residue is 60 DEG C/1Under mbar dry 2.5 hours, be then dissolved in hexane (125ml), and at 5 DEG C store overnight. Filter the crystal obtainingMatter, washs and is dried with cold hexane (20ml). Productive rate: 8.97g (10.6mmol, 69%).1H-NMR(CD2Cl2):δ1.17(s，9H)，1.30(s，9H)，1.51(s，9H)，1.56(s，9H)，3.81(s，3H)，3.85(2s，6H)，3.86(3H)，6.71(d，1H)，6.74(d，1H)，6.81(d，1H)，6.83(d，1H)，6.95(d，1H)，7.04(d，1H)，7.06(d，1H)，7.09(d，1H)ppm。EI-MS，m/e809(2%，[M-Cl]+)；727(100%)。
Compound 22
The solution of 1 (1.0g, 1.001mmol) in toluene (6ml) under the gentle agitation of chamber with triethylamine (0.28Ml, 2.002mmol) mix, then at 0 DEG C with phosphorus trichloride (0.152g, 1.1mmol) molten in toluene (2ml)Liquid mixes. Be warming up to after room temperature, stir and spend the night and filter, in a vacuum except desolventizing. Residue stirs 16 with 10ml hexaneHour and filter residue under 50 DEG C/0.1KPa dry 3 hours. Productive rate: 0.86g (0.781mmol, 78%).31PNMR(CD2Cl2):δ102.8(s)，103.5(s)，103.9(d)，134.9(s，br)，198.7(s)，199.3(s)，203.3(d) ppm (non-enantiomer mixture). Total intensity in each desired extent is corresponding to the ratio of 3 phosphorus atoms 1:1:1Example.
Compound 23
Molten in toluene (9ml) of 2 (0.6g, 0.545mmol) and triethylamine (0.109g, 1.087mmol)Liquid under agitation dropwise mixes at 0 DEG C with the solution of PCl3 (0.070g, 0.516mmol) in toluene (2ml). In chamberAfter the lower stirring of temperature is spent the night, filtering reacting solution, filtrate is concentrated into dry in a vacuum. Residue is dry under 50 DEG C/0.1KPa3 hours, and be used in ensuing synthesis step and there is no further purifying.31PNMR(CD2Cl2):δ100.9(dd，JPP=71Hz；4Hz)，102.9(s，br)，103.4(dd，JPP=3Hz；3Hz)，135.2(s，br)，135.7(dd，JPP=8Hz，4Hz)，135.9(s，br)，199.9(dd，JPP=71Hz，8Hz)，203.1(d，JPP=3Hz)，203.2(s，br)。
Compound 24
By making corresponding phosphite ester phenol (D.Selent, D.Hess, K.-D.Wiese, D.R ttger, C.Kunze, A.B rner, Angew.Chem.2001,113,1739) and PCl3Reaction, by the method preparationization that is similar to 21Compound 24. Crude product after dry 2 hours, obtains pure material according to spectrum with hexane washing and under 50 DEG C/0.1KPa. ProduceRate: 72%.1HNMR(CD2Cl2):δ1.11(s，9H)，1.27(s，9H)，1.36(s，9H)，1.38(s，9H)，1.40(s，9H)，1.41(s，9H)，1.52(s，9H)，1.58(s，9H)，7.14(d，JHH=2.5Hz，1H)，7.16(d，JHH=2.5Hz，1H)，7.24(d，JHH=2.5Hz，1H)，7.31(d，JHH=2.5Hz，1H)，7.39(d，JHH=2.5Hz，1H)，7.50(d，JHH=2.5Hz，1H)，7.53(d，JHH=2.5Hz，1H)，7.55(d，JHH=2.5Hz，1H)ppm。
NMR-spectrum test stability
Ligand 17 and bidentate contrast ligand Biphephos are dissolved in respectively to untreated toluene-D8In, shiftEnter in NMR tubule and sealing. Follow the trail of ligand content 32 days by NMR spectrum.
Result is shown in Figure 1. As clear demonstration in Fig. 1, compared with contrast ligand Biphephos, coordinationBody 17 has obviously higher stability. In fact,, after 32 days, contrast ligand Biphephos no longer can be surveyed by NMRArrive, and ligand 17 is measured to the concentration having with respect to initial value 60%.
From respectively to can eduction going out accordingly to urge this stability test of free ligand 17 and BiphephosChange active compound, the stability of the rhodium complex derivative for example being formed by it. For grasping with this catalytic activity compositionThe hydroformylation process of doing, this means that obviously extend the running life of the catalytic activity composition based on ligand 17,And be optimised economically thus. Realizing this does not need further stabilisation component, for example, in EP2280920The huge sterically hindered amine derivative adding. Different alkene or containing the ensuing catalysis test of the hydrocarbon flow of different alkene in detailCarefully prove this technology instruction.
The checking structure of three tooth features
The rhodium complex of preparation ligand 17, and to be applicable to the mass separation of X ray. The structure being obtained by X ray picture asUnder:
。
Obtain data acknowledgement rhodium at PIIIOn 3 reprovision positions. Therefore this solution contains potential higher on transition metalPIIIConcentration, and there is following result:
● rhodium is retained in solution better, therefore with the form of catalytic activity composition, and
● the aggregation that has suppressed the rhodium of describing in document forms.
Compared with in bidentate system, the tendency that ligand dissociation and aggregation form is less, provides and has urged thusAgent active compound compared with the long running life-span.
Three tooth features are as the checking structure of dual-core architecture form
The rhodium complex of preparation ligand 17, and to be applicable to the mass separation of X ray. The structure being obtained by X ray picture asUnder:
。
The data that obtain have confirmed the structure of the double-core rhodium complex in catalytic activity composition in addition. Therefore provedThe stabilisation of the second rhodium atom of the each complex in catalytic activity composition, and thereby prevented in addition aggregation formation,, the loss of rhodium.
For novel ligand, initial requirement have following some:
● intrinsic catalyst poison is there is to the resistance of improvement, and
● by suppressing the formation of rhodium aggregation with multiple coordination and the formation binuclear complex of terdentate ligand, this passes throughProvide compound of the present invention also to realize as ligand with them.
In alkene being also had to the catalysis test containing alkene mixture below, disclose, compound according to the present invention is being urgedChange the ability that is used as ligand hydroformylation in active compound.
The operating provision of catalysis test
Hydroformylation is being equipped with the pressure regulator of the pressure that keeps constant, gas flowmeter, jet agitationIn the 200ml autoclave of device and pressure pipette, implement. The impact bringing in order to minimize moisture and oxygen, not only dry solvent(Tol=toluene, PC=propylene carbonate, THF=oxolane), also wants dry matrices. For this test, under argon gas toIn autoclave filling as catalyst precarsor with [(acac) Rh (COD)] (acac=acetylacetonate anion; COD=1,5-cyclo-octadiene) rhodium of the form solution in toluene. Then mix the phosphite ester chemical combination of the toluene dissolving of respective amountThing, common each rhodium 2-5 ligand equivalent. Measure the quality of each toluene of introducing. Weighing of alkene: 1-octene(10.62g, 94.64mmol), positive octene (10.70g, 95.35mmol), 2-amylene (2.81g, 40.0mmol, its spyLevy and be in following table, to there is " (P) ", or 9.75g, 139.00mmol). Add in a similar manner 1-butylene, 2-butyleneAnd isobutene. Under stirring (1500rpm), be 4.2MPa at a) final pressure for 5.0MPa; B) for 2.0MPaFinal pressure be 1.2MPa; And c) for the final pressure of 1.0MPa be under total gas pressure of 0.7MPa (synthesis gas:H2(99.999%):CO2(99.997%)=1:1), autoclave is heated to the concrete temperature of reporting. Reaching reaction temperatureAfter degree, it is 4.85MPa, b that synthesis gas pressure is increased to a) final pressure for 5.0MPa) for 2.0MPa'sFinal pressure is 1.95MPa and c) is 0.95MPa for the final pressure of 1.0MPa, and is set as in pressure pipetteUnder the overvoltage of about 0.3MPa, inject the concrete alkene of table report or contain alkene mixture. Be respectively 5.0,2.0 and 1.0Under the constant pressure of MPa, implement this reaction 4 hours. After reaction time finishes, autoclave is cooled to room temperature, decompression under stirringAnd clean with argon gas. After turning off agitator, take out immediately the 1ml sample of every kind of reactant mixture, use 5ml pentane to dilute alsoPass through gc analysis: HP5890SeriesIIplus, PONA, 50mx0.2mmx0.5 μ m. Aldehyde and residualThe quantitative assay of remaining alkene is with respect to carrying out as interior target solvent toluene.
The catalysis test of compound 6-17
Productive rate=based on alkene used or containing the productive rate of alkene mixture
Sel. (%)=just selective (%)
1-octene
Ligand P(MPa) T(℃) t (h) [Rh](ppm) L/Rh Solvent Productive rate (%) Sel.(%)
7 5.0 100 4 40 1 Tol 85 95.8
7 5.0 100 4 40 2 Tol 86 95.5
9 5.0 100 4 40 2 Tol 86 94.9
9 5.0 100 4 40 2 PC 84 95.0
10 5.0 100 4 40 2 Tol 87 95.6
15 5.0 100 4 40 2 Tol 86 96.1
11 5.0 100 4 40 2 Tol 90 97.2
16 5.0 100 4 40 2 Tol 90 91.0
17 5.0 100 4 40 4 Tol 91 89.5
The all ligands that use are all three teeth, and in reaction, show good to outstanding productive rate and separatelyOutstanding is just selective. As the L/Rh ratio showing in table, each catalytic activity composition only needs low ligand excessiveJust can realize this effect.
Positive octene(1-octene: 3.3%, cis+trans-2-octene: 48.5%, cis+trans-3-octene: 29.2%,Cis+trans-4-octene: 16.4%, the octene of structural isomerism: 2.6% octene isomers mixture)
Ligand P(MPa) T(℃) t (h) [Rh](ppm) L/Rh Solvent Productive rate (%) Sel.(%)
7 2.0 120 4 100 1 Tol 68 84.2
7 2.0 120 4 100 2 Tol 79 85.5
7 2.0 120 4 100 10 Tol 74 85.6
8 2.0 120 4 100 2 PC 85 87.1
17 2.0 120 4 100 2 Tol 76 84.4
The all ligands that use are all three teeth, and in reaction, show good to outstanding productive rate and separatelyOutstanding is just selective. As the L/Rh ratio showing in table, each catalytic activity composition only needs low ligand excessiveJust can realize this effect. As illustrated in the example of ligand 7 in table, higher ligand is excessive is unnecessary.
2-amylene(15ml，2.41M)
(P) represent to use lower 2-amylene (referring to above)
Ligand P (MPa) T (℃) t (h) [Rh] (ppm) L/Rh Solvent Productive rate (%) Sel. (%)
7 2.0 120 4 100 1 Tol 93 (P) 89.6
7 2.0 120 4 100 1 PC 87 (P) 91.6
7 2.0 120 4 100 2 Tol 95 (P) 90.2
7 2.0 120 4 100 2 PC 93 (P) 92.4
7 2.0 120 4 100 2 PC 90 92.2
7 2.0 120 4 100 5 Tol 95 90.0
7 2.0 120 4 100 10 Tol 95 (P) 90.4
7 2.0 120 4 100 2 Tol 94 89.7
7 2.0 120 4 120 1.7 Tol 96 89.9
7 2.0 120 4 100 2/ 2 TINUVIN? Tol 96 90.2
7 2.0 100 4 100 2 PC 89 91.7
7 2.0 100 4 100 2 Tol 91 90.5
7 2.0 120 4 100 2 Tol 94 89.7
8 2.0 120 4 100 2 PC 95 92.7
8 2.0 120 4 100 5 PC 92 92.6
8 2.0 120 4 100 10 PC 95 92.6
8 2.0 120 4 100 2 Tol 95 90.6
8 2.0 120 4 100 2 THF 94 91.0
8 1.0 120 4 100 2 PC 92 90.7
8 2.0 100 4 100 2 PC 93 92.0
8 2.0 110 4 100 2 PC 94 92.4
10 2.0 120 4 100 2 PC 92 92.6
10 2.0 120 4 100 2 Tol 95 90.2
10 2.0 120 4 100 5 Tol 95 90.2
10 2.0 100 4 100 2 PC 90 92.8 19 -->
11 2.0 120 4 100 2 Tol 95 (P) 93.8
11 2.0 120 4 100 2 Tol 96 93.9
11 2.0 120 4 100 2 PC 93 (P) 94.3
11 2.0 120 4 100 1 Tol 91 (P) 93.4
11 2.0 120 4 100 5 Tol 95 (P) 94.4
11 1.0 120 4 100 2 Tol 96 93.6
11 1.0 110 4 100 2 Tol 91 94.1
11 2.0 120 4 100 2 PC 99 94.4
11 1.0 110 4 100 2 PC 94 95.1
11 1.0 100 4 100 2 PC 90 95.8
11 2.0 100 4 100 2 PC 87 93.9
12 2.0 120 4 100 2 Tol 97 90.4
12 2.0 120 4 100 2 PC 97 91.9
12 1.0 100 4 100 2 PC 87 94.2
13 2.0 120 4 100 2 PC 89 94.5
13 1.0 110 4 100 2 PC 84 95.6
13 1.0 110 4 100 2 PC 91 95.4
14 2.0 120 4 100 2 Tol 88 (P) 89.7
15 2.0 120 4 100 2 PC 95 92.6
15 2.0 120 4 100 2 Tol 91 90.1
6 2.0 120 4 100 2 Tol 65 88.6
17 2.0 100 4 100 2 Tol 87 89.6
17 2.0 120 4 100 2 Tol 93 90.8
17 2.0 120 4 100 5 Tol 97 90.2
17 2.0 120 4 100 2 PC 97 91.8
Compared with other series of testing, the catalysis test of the 2-amylene of specific series has 2 specific characteristics:
● in ligand 6, use bidentate compound, wherein, compared with used other ligand, be recorded toThe obvious decline of productive rate;
● in a test, (trade mark is TINUVIN to terdentate ligand 7 with the amine derivative of huge steric hindrance?=bis--4-(2,2,6,6-tetramethyl) piperidyl sebacate) reaction, wherein do not obtain better at productive rate with just selectivelyResult.
C-4-alkene
Ligand Matrix P (MPa) T (℃) t (h) [Rh] (ppm) L/Rh Solvent Productive rate (%) Sel. (%)
17 2-butylene 2.0 120 5 40 3.9 Toluene 93.8 90.2
17 1-butylene 2.0 120 5 37 6.0 Toluene 82.2 87.8
17 Isobutene 2.0 100 5 38 6.0 Toluene 64.6 100

Claims (21)

1. compound, it comprises structural element (I):
And,
-described compound comprises at least two O-PIIIKey, wherein these O-PIIIKey can produce from identical PIIIOr produce certainlyDifferent PIII；
If-structural element (I) occurs twice in described compound, below they pass through C10-C10 ' carbon bond or pass through soX1-G1-X2Unit is connected to each other:
Wherein X1Be connected to the P of the first structural element (I)III, and X2Be connected to the P of the second structural element (I)III，
Wherein G1Comprise structural element (V):
Wherein R51、R52、R53、R54、R55、R56、R57、R58=hydrogen; There is the straight or branched of the further replacement of any hopeThe alkyl of aliphatic series; F, Cl, Br or I; Or-OR59；
Wherein R59Be selected from: hydrogen, replacement or unsubstituted, straight or branched, the alkyl of aliphatic series;
And there is a and b as being connected to X1And X2Tie point;
Wherein X1、X2O;
Wherein R1、R2、R3、R4、R5、R6、R7Hydrogen.
2. compound according to claim 1,
It comprises structural element (II):
Wherein W is selected from:
-hydrogen;
-PIII(G2)(G3) group:
Wherein G2And G3Be-OR18；
Wherein R18Be selected from: hydrogen, replacement or unsubstituted, straight or branched, the alkyl of aliphatic series or aromatics;
Can be wherein G2And G3The implication of selecting is independently each other, and G2And G3Can covalently connect each otherConnect,
-SiR28R29R30; Wherein R28、R29、R30=hydrogen; There is the straight or branched of the further replacement of any hope, aliphatic seriesAlkyl; Can be wherein R28、R29And R30The implication of selecting is independently each other, and R wherein28And R29Each otherCan covalently connect.
3. compound according to claim 2,
It comprises structural element (III):
Wherein Z represents G4Or X1-G1-X2Unit,
And G4Xuan Zi – OR31，
Wherein R31Be selected from: replacement or unsubstituted, straight or branched, the alkyl of aliphatic series or aromatics.
4. compound according to claim 2,
It comprises structural element (IV):
Wherein G5And G6Be selected from :-OR41，
Wherein R41Be selected from: hydrogen, replacement or unsubstituted, straight or branched, the alkyl of aliphatic series or aromatics;
Can be wherein G5And G6The implication of selecting is independently each other, and G5And G6Can covalently connect each otherConnect.
5. according to the compound described in claim 2-4 any one,
Wherein W represents PIII(G2)(G3) group.
6. according to the compound described in claim 2-4 any one,
Wherein G2And G3Covalently connect each other.
7. according to the compound described in claim 2-4 any one,
Wherein said connection G2-G3Comprise following structural element (VI):
Wherein R69、R70、R71、R72、R73、R74、R75、R76=hydrogen; There is the straight or branched of the further replacement of any hope,The alkyl of aliphatic series; F, Cl, Br or I; Or-OR77；
Wherein R77Be selected from: hydrogen, replacement or unsubstituted, straight or branched, the alkyl of aliphatic series or aromatics.
8. compound according to claim 4,
Wherein G5And G6Covalently connect each other.
9. compound according to claim 4,
Wherein said connection G5-G6Comprise following structural element (VII):
Wherein R87、R88、R89、R90、R91、R92、R93、R94=hydrogen; There is the straight or branched of the further replacement of any hope,The alkyl of aliphatic series; F, Cl, Br or I; Huo – OR95；
Wherein R95Be selected from: hydrogen, replacement or unsubstituted, straight or branched, the alkyl of aliphatic series.
10. compound according to claim 4,
Wherein PIII(G2)(G3) group according to structural formula corresponding to PIII(G5)(G6) group.
11. complexs, comprising:
-according to the compound described in claim 1-10 any one,
-at least one central metal atom,
Wherein said compound is by least one PIIIBe coordinated on central metal atom.
12. complexs according to claim 11,
Wherein said central metal atom is selected from the 8-10 family of the periodic table of elements.
13. complexs according to claim 12, wherein said central metal atom is rhodium.
14. compositions, comprising:
-be not coordinated on central metal atom according to the compound described in claim 1-10 any one, and
-according to the complex described in claim 11-13 any one.
15. compositions according to claim 14 are the use in organic compound synthetic as catalytic activity compositionOn the way.
16. compositions according to claim 14 as catalytic activity composition for ethylenically unsaturated hydrocarbons mixturePurposes in the method for hydroformylation.
17. multi-phase reaction mixtures, contain:
-ethylenically unsaturated hydrocarbons mixture,
-containing the admixture of gas of carbon monoxide and hydrogen,
-aldehydes,
-according to the composition as catalytic activity composition described in claim 14.
18. to prepare the method for aldehydes, described method comprises following for the hydroformylation of ethylenically unsaturated hydrocarbons mixtureStep:
A) provide the mixture of ethylenically unsaturated hydrocarbons class;
B) add catalytic activity composition as claimed in claim 14;
C) introduce the mixture that comprises carbon monoxide and hydrogen;
D) heat the temperature range of this reactant mixture to 80 DEG C-120 DEG C;
E) pressure limit of construction 1.0MPa-6.4MPa;
F) finishing to isolate ethylenically unsaturated hydrocarbons mixture after reaction.
19. methods according to claim 18,
It comprises further step:
G) unconverted ethylenically unsaturated hydrocarbons mixture is isolated and is back to step a) in.
20. according to the method described in claim 18 or 19 any one,
It comprises further step:
H) catalytic activity composition as claimed in claim 19 is isolated and is back to step b) in.
21. according to the method described in claim 18 or 19 any one,
It comprises further step:
I) the unconverted admixture of gas containing carbon monoxide and hydrogen is isolated and is back to step c) in.
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